Photolytic degradation of triclosan in freshwater and seawater

A 12-days photolysis experiment of triclosan, a widely used bactericide, was performed in freshwater and seawater under a low intensity artificial white light source. Photodegradation of triclosan was observed in both the freshwater and seawater samples. Assuming a first-order reaction, half-lives of triclosan in the freshwater and seawater were approximately 8 and 4 days, respectively. 2,8-Dichlorodibenzo-p-dioxin (DCDD) was detected in both the freshwater and seawater samples after 3 days of irradiation. The photodegradation of triclosan and the production of DCDD suggest that triclosan could be less stable and DCDD might be more stable in seawater than freshwater. As a result, DCDD produced from triclosan survives for a longer time in seawater.     

Photochemical behaviour of carbendazim in aqueous solution

To elucidate the photochemical behaviour of carbendazim (or MBC) in superficial waters, photolysis studies have been carried out in aqueous solutions at several pH using a UV light source (high pressure mercury arc lamp) or a solar light simulator (xenon arc lamp). The kinetics of photodecomposition of carbendazim was determined using HPLC-DAD and the identification of photoproducts was carried out with HPLC-MS (ESI negative and positive mode). According to the experimental results carbendazim is a rather stable molecule in the dark or in environmental conditions. The pH influence of the environmental medium on the photodegradation rate has been confirmed. The photochemical process can be considerably accelerated in alkaline solutions using HPK-quartz irradiation (quantum efficiency at pH 9 phi = 3.1 x 10(-3) degraded molecule per absorbed photon) while the photodegradation is not as efficient under a simulated sun irradiation (quantum efficiency in the suntest phi = 10(-4) at pH 7). Three photoproducts have been tentatively identified in pure water: 2-aminobenzimidazole, benzimidazole isocyanate and monocarbomethoxy-guanidine (issued from the cleavage of the benzimidazole ring). The last one seems very stable and could be accumulated in the environment.     

太阳光对湖泊中有机污染物降解的研究进展

论述了太阳光对湖泊水体中有机污染物降解作用的研究,就其降解机理、动力学特征、作用对象及降解产物等作了逐一介绍.阐明了太阳光对生物降解湖泊水体中有机污染物具有协同作用,也概述了光降解作用受pH、溶解性有机物(DOM)、水深与水体运动、地理、水文、水质与气候等因素的影响.并对实验室模拟条件下的降解与自然条件下的降解进行对比,提出今后该领域的发展前景与研究方向.     

铁(Ⅲ)-草酸盐配合物的光化学性质及其对天然水相中有机物光降解的作用

本文综述了天然水相（大气水相、地表水等）中Ｆｅ（Ⅲ）－草酸盐配合物的含量与分布、光化学性质、对天然水相中有机物的降解、及其在废水光化学处理中的应用研究及前景。     

Photodegradation of pentachlorophenol by sunlight in aquatic surface microlayers

Photodegradation of pentachlorophenol (PCP) in aquatic surface microlayer (SM) was examined under natural sunlight. SM samples were collected using a glass plate, along with corresponding subsurface waters. PCP was added to samples of the SM and subsurface water. When all samples were exposed to the same natural sunlight conditions, the first order photodegradation rates of PCP in the SM water samples were different from those of PCP in corresponding subsurface water samples. The difference was correlated with the enrichment of dissolved organic carbon (DOC) in SM compared to the corresponding subsurface waters. Enhanced photodegradation in SM may be due to increased abundance of photoreactants related to the UV-absorbing properties of dissolved organic materials in the SM as the result of photo-induced reactions. Effects of environmental factors, pH and salinity, on photodegradation process of PCP in SM were also evaluated.     

Photodegradation of the synthetic fragrance OTNE and the bactericide triclosan adsorbed on dried loamy sand--results from models and experiments

Fragrances such as OTNE (marketed as Iso-E-Super®) and bactericides such as triclosan (marketed as Igrasan) are present in waste water and thus finally sorbed to sewage sludge. With that sludge they can reach agricultural fields where they potentially can undergo photodegradation processes. In this study the photodegradation of OTNE and triclosan on dried loamy sand was measured under artificial sunlight conditions in laboratory experiments. These compounds were artificially added with concentrations of 1 μg g⁻¹ on pre-rinsed dried loamy sand. The decrease in concentration with light irradiation was measured for 32 d in comparison to soil samples without light irradiation. The estimated light source intensity was 27 W m⁻². Within the experiment, the apparent half-life was 7 and 17 d for OTNE and triclosan respectively. The decrease did not simply follow first-order kinetics. The apparent rate constant decreased in the latter stage of reaction, suggesting that part of the chemicals were inaccessible for degradation. Two models, i.e., a diffusion-limited model, and a light penetration-limited model, were used in comparison to the measured data to explain the observed degradation limitations in the latter stages of the experiments. Comparing the hereby obtained model parameters with estimated physico-chemical parameters for the soil and the two chemical compounds, the light penetration-limited model, in which the degradation in the soil surface layer is assumed to be limited due to the shading effect of light in the upper thin soil layer, showed to be the most realistic in describing the photodegradation.     

Effects of photodegradation of dissolved organic matter on the binding of benzo(a)pyrene

Dissolved organic matter (DOM) in natural waters can bind various organic pollutants, and the affinity of this binding is strongly influenced by the chemical characteristics of the DOM and water pH. This study examined the effects of photochemically induced alteration of the DOM's chemical properties and water pH on the binding of benzo(a)pyrene (BaP). Time- and pH-series of solar-simulated irradiations were performed on a natural water sample and aqueous DOM solutions prepared from aquatic and soil humic substances. The binding affinity of BaP, expressed as a partition coefficient of a compound to DOM, decreased substantially after the DOM samples were irradiated over environmentally relevant radiation doses and pH ranges. The lowering of the pH due to the photoproduction of acidic products often partly offsets the reduction of the binding affinity caused by direct photoalteration of the DOM's chemical structure. The decrease of the binding affinity, after correction for the photoinduced pH change, was positively correlated with the decrease in the molecular weight and the aromaticity of the DOM in the course of irradiation. Increasing O(2) abundance accelerated the decrease of the binding affinity as a result of enhanced DOM photodegradation. Visible light played a more important role in reducing the molecular weight and aromaticity of the DOM than in reducing the content of dissolved organic carbon (DOC) via photoremineralization while the reverse was true for UV radiation, indicating that photochemical reduction of the binding affinity may occur in natural waters at depths greater than UV radiation can reach. A decrease of the affinity of DOM for binding BaP will increase the free dissolved fraction of BaP and thus its availability and toxicity to aquatic organisms. The results from this study may have similar implications for organic pollutants other than BaP.     

硝酸根紫外光降解对硝基苯甲酸的研究

以硝酸铝做光氧化剂,研究了紫外光照射下,NO-3对PNB(对硝基苯甲酸)的光降解作用.探索了NO-3投加量、模拟废水初始浓度和pH值、光照时间、溶解氧浓度对处理效果的影响.结果表明,NO-3对PNB具有良好的光氧化作用,在最佳处理条件下,NO-3光降解PNB 4 h后降解率达90.8%.廉价硝酸盐对于有机物能起到显著光...     

Nano-MnO<Subscript>2</Subscript>-mediated transformation of triclosan with humic molecules present: kinetics,products, and pathways

It has been shown that manganese dioxide (MnO₂) can mediate transformation of phenolic contaminants to form phenoxyl radical intermediates, and subsequently, these intermediates intercouple to form oligomers via covalent binding. However, the reaction kinetics and transformation mechanisms of phenolic contaminants with humic molecules present in nano-MnO₂-mediated systems were still unclear. In this study, it was proven that nano-MnO₂ were effective in transforming triclosan under acidic conditions (pH 3.5–5.0) during manganese reduction, and the apparent pseudo first-order kinetics rate constants (k?=?0.0599–1.5314 h^?1) increased as the pH decreased. In particular, the transformation of triclosan by nano-MnO₂ was enhanced in the presence of low-concentration humic acid (1–10 mg L^?1). The variation in the absorption of humic molecules at 275 nm supported possible covalent binding between humic molecules and triclosan in the nano-MnO₂-mediated systems. A total of four main intermediate products were identified by high-resolution mass spectrometry (HRMS), regardless of humic molecules present in the systems or not. These products correspond to a suite of radical intercoupling reactions (dimers and trimers), ether cleavage (2,4-dichlorophenol), and oxidation to quinone-like products, triggered by electron transfer from triclosan molecules to nano-MnO₂. A possible reaction pathway in humic acid solutions, including homo-coupling, decomposition, oxidation, and cross-coupling, was proposed. Our findings provide valuable information regarding the environmental fate and transformation mechanism of triclosan by nano-MnO₂ in complex water matrices.     

Photochemical behavior of fenpropathrin and λ-cyhalothrin in solution

The photodegradation processes of fenpropathrin and λ-cyhalothrin were studied in hexane, methanol/water (1:1, v/v), and acetone in both ultraviolet light and simulated sunlight. Intermediates in the photodegradation process were identified using gas chromatography/mass spectrometry (GC/MS), and the analysis of intermediates was used to speculate on possible photodegradation pathways. The photodegradation processes of fenpropathrin and λ-cyhalothrin followed pseudo first-order kinetics. The photodegradation rates varied according to the solvent in decreasing order: hexane?>?methanol/water (1:1, v/v)?>?acetone. The effects of substances coexisting in the environment on the photodegradation of pyrethroids were also investigated in the research. Acetone, humic acid, and riboflavin increased photodegradation rates while l-ascorbic acid slowed the process. This study provides a theoretical basis for the removal of pyrethroid pollution from the natural environment.     

Evaluation of the Use of Solar Irradiation for the Decontamination of Soils Containing Wood Treating Wastes

Laboratory evaluation of the efficacy of soil phase photodegradation of recalcitrant hazardous organic components of wood treating wastes is described. The photodecomposition of anthracene, biphenyl, 9H-carbazole, m-cresol, dibenzofuran, fluorene, pentachlorophenol, phenanthrene, pyrene and quinoline under UV and visible light was monitored over a 50-day reaction period in three test soils. Methylene blue, riboflavin, hydrogen peroxide, peat moss and diethylamine soil amendments were evaluated as to their effect on the enhancement of compound photoreaction rates in the test soil systems. Dark control samples monitored over the entire study period were utilized to quantify non-photo mediated reaction losses. Compounds losses in both the dark control and irradiated samples were found to follow first order kinetics, allowing the calculation of first order photodegradation reaction rate constants for each test soil/compound combination. Degradation due to photochemical activity was observed for all test compounds, with compound photolytic half-lives ranging from 7 to approximately 180 days. None of the soil amendments were found to improve soil phase photodegradation, although photosensitization by anthracene was shown to significantly enhance the rate of photodegradation of the other test compounds. Soil type, and its characteristic of internal reflectance, proved to be the most significant factor affecting compound degradation rates suggesting the necessity for site specific assessments of soil phase photodegradation potential.     

Sorption and degradation of imidacloprid in soil and water

Imidacloprid, the major component of many widely used insecticide formulations, is highly persistent in soils. In this study, the sorption of imidacloprid by six soils as well as its photodegradation and hydrolysis in water were studied. The soils differed significantly in organic matter content and other physical and chemical properties. Sorption increased with increasing soil organic matter content but was not significantly correlated with other soil properties. Removal of organic matter via H2O2 oxidation decreased the sorption. By normalizing the Freundlich coefficients (Kf) to organic matter contents, the variability in obtained sorption coefficient (Kom) was substantially reduced. These results indicate that soil organic matter was the primary sorptive medium for imidacloprid. The low heat of sorption calculated from Kom suggests that partition into soil organic matter was most likely the mechanism. The photodegradation and hydrolysis of imidacloprid in water followed pseudo-first-order kinetics; however, the latter process needed a six-time-higher activation energy. While both processes produced the same main intermediate, they occurred via different pathways. The hydrolysis of imidacloprid was not catalyzed by the high interlayer pH in the presence of metal-saturated clays, which appeared to result from the lack of the pesticide adsorption in the interlayers of clays.     

Photochemistry of hydrolytic iron (III) species and photoinduced degradation of organic compounds. A minireview

On the basis of the research literature of the last fifty years, we have reviewed the photochemical properties of different hydrolytic Fe(III) species and the photodegradation of organic compounds in aqueous solutions initiated by them (mainly including low-molecular-weight Fe(III)-OH complexes, Fe(III) oxides (Fe2O3) and Fe(III) hydroxides (FeOOH)). Furthermore, the feasibility and prospects of the novel photochemical methods of using Fe(III) salts and oxides in wastewater treatments are being discussed in this paper.     

Photolytic degradation of quinalphos in natural waters and on soil matrices under simulated solar irradiation

The photochemical persistence of quinalphos, one of the most widely used organophosphorous insecticides, was investigated in a variety of environmental matrices such as natural waters and soils of different composition. Simulated solar irradiation was obtained using a xenon arc lamp (Suntest CPS+ apparatus) giving an irradiation intensity of 750 W m(-2) equivalent to a light dose per hour of irradiation of 2,700 kJ m(-2). The phototransformation rates were determined using solid-phase microextraction (SPME) and ultrasonic extraction (USE) coupled to GC-FTD, while the identification of photoproducts was carried out by GC-MS. In water samples, the degradation kinetics followed a pseudo-first-order reaction and photolysis half-lives ranged between 11.6 and 19.0 h depending on the constitution of the irradiated media. Dissolved organic matter (DOM) has a predominant retarding effect, while nitrate ions accelerated the photodegradation kinetics. In soil samples, the degradation kinetics was monitored on 1mm soil layer prepared on glass TLC plates. The kinetic behaviour of quinalphos was complex and characterized by a double step photoreaction, fast in the first 4h of irradiation followed by a slow degradation rate up to 64 h. The photolysis half-life of quinalphos was shorter in sandy soil compared to the rest of the soil samples, varying between 16.9 and 47.5 h, and showing a strong dependence on the composition of the irradiated media. Among the transformation products formed mainly through photohydrolysis and photoisomerization processes, some photoproduct structures were proposed according to their mass spectral information.     

Determinations and residual characteristics of triclosan in household food detergents of Taiwan

Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether) is a widely used antibacterial agent. However, it was concerned recently that triclosan might act as an antibiotic and will cause resistant bacterial strains. Furthermore, possible formation of toxic chloroform was also reported when the triclosan contained in household dishwashing soaps reacted with the chlorinated water. To assess the associate risks from possible exposures, concentrations of triclosan in household food detergents of Taiwan were determined in this study. High performance liquid chromatography (HPLC) with UV detector at 280 nm was used to analyze the triclosan in samples. Factors that might affect the residual characteristics of triclosan from detergents on dishware and fruits, including the concentrations of detergents used, the temperature and immersion time for water before the cleaning processes, the temperatures of water used for the cleaning processes, and the materials of dishware made of, were evaluated under the orthogonal experiment design by the Taguchi method. By the analysis of variance, the orders of importance of different parameters were determined. The concentrations of triclosan detected in household food detergents were found to be 1.7 x 10(-2) -5.6 x 10(-1) (triclosan/detergent, mg g(-1)). For residual characteristics, the concentration of detergents used as well as the materials of dishware were found to be the significant factors that will affect the triclosan left on the dishware. On the other hand, the concentration of triclosan in the detergents was found to be the only factor that will affect the triclosan left on fruits. The maximum dose of triclosan exposures from the use of household food detergents in Taiwan was also estimated in the study.     

水中四环素类化合物在不同光源下的光降解

研究了模拟太阳光和实际室外太阳光下四环素类化合物在水溶液中的光降解。结果表明,四环素类化合物(TCs)在模拟太阳光照射下均能发生直接光降解,且其降解速率随pH不同变化很大。四环素(TC)、土霉素(OTC)、金霉素(CTC)和多西环素(DTC)的光降解速率随溶液pH升高明显加快,而米诺环素(MTC)在水中的光降解速率随溶液pH升高略有下降。天然水体pH范围内,模拟太阳光照下四环素类化合物表观光降解速率常数在0.004～0.026 min-1范围内,降解半衰期在26～136 min范围内。在室外实际太阳光照下,四环素类化合物光降解反应速率与太阳光强成正比例关系。晴朗无云天气下,四环素类化合物降解半衰期在春冬季节较长、夏季节较短;四环素在东江实际水体中表观光降解速率很快,在冬季晴天天气下,其平均半衰期仅为8.2 min。     

Nitrate-induced photodegradation of atenolol in aqueous solution: kinetics, toxicity and degradation pathways

The extensive utilization of β-blockers worldwide led to frequent detection in natural water. In this study the photolysis behavior of atenolol (ATL) and toxicity of its photodegradation products were investigated in the presence of nitrate ions. The results showed that ATL photodegradation followed pseudo-first-order kinetics upon simulated solar irradiation. The photodegradation was found to be dependent on nitrate concentration and increasing the nitrate from 0.5 mM L⁻¹ to 10 mM L⁻¹ led to the enhancement of rate constant from 0.00101 min⁻¹ to 0.00716 min⁻¹. Hydroxyl radical was determined to play a key role in the photolysis process by using isopropanol as molecular probe. Increasing the solution pH from 4.8 to 10.4, the photodegradation rate slightly decreased from 0.00246 min⁻¹ to 0.00195 min⁻¹, probably due to pH-dependent effect of nitrate-induced OH formation. Bicarbonate decreased the photodegradation of ATL in the presence of nitrate ions mainly through pH effect, while humic substance inhibited the photodegradation via both attenuating light and competing radicals. Upon irradiation for 240 min, only 10% reduction of total organic carbon (TOC) can be achieved in spite of 72% transformation rate of ATL, implying a majority of ATL transformed into intermediate products rather than complete mineralization. The main photoproducts of ATL were identified by using solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) techniques and possible nitrate-induced photodegradation pathways were proposed. The toxicity of the phototransformation products was evaluated using aquatic species Daphnia magna, and the results revealed that photodegradation was an effective mechanism for ATL toxicity reduction in natural waters.     

Fate of pharmaceuticals--photodegradation by simulated solar UV-light

The fate of pharmaceuticals in surface waters under solar irradiation was investigated. Photodegradation of pharmaceuticals caused by sun irradiation may be of major significance in the natural elimination process. Based on a data compilation from the literature, the lipid lowering agent metabolite clofibric acid, the iodinated X-ray contrast media iomeprol, which contribute to the adsorbable organic halogen compounds, and the antiepileptic drug carbamazepine were selected. The irradiation experiments were carried out in batch experiments with simulated UV–sunlight. The photodegradation of the pharmaceuticals showed a pseudo-first-order kinetics. The objective of this investigation was to demonstrate that the extent of photoinduced degradation of pharmaceuticals can vary significantly for the different pharmaceuticals and it strongly depends on the water constituents present in solution. The influences of different initial pharmaceutical concentrations, the presence of other pharmaceuticals like carbamazepine or clofibric acid and the presence of natural organic matter on the photochemical degradation rate of pharmaceuticals in aqueous solutions were investigated. Analyses of the pharmaceuticals and their photodegradation products were carried out by high performance liquid chromatography with diode-array and fluorescence detection.     

Effects of Fe2O3, organic matter and carbonate on photocatalytic degradation of lindane in the sediment from the Liao River,China

Fourteen sediment samples with different content of Fe₂O₃ were collected from the lower reaches of the Liao River in China. The photodegradation of lindane on the surfaces of these sediments was investigated to observe the effects of Fe₂O₃ and other photoinducable substances, such as TiO₂ and organic substances, on photodegradation of lindane. A partial least-squares (PLS) analysis model was developed to find out the statistical relationship between the photodegradation and the contents of these photoinducable substances. It was concluded from the PLS analysis that inorganic carbon and organic carbon have negative effects, whereas Fe₂O₃ and TiO₂ accelerate the photodegradation of lindane in the sediment samples when 365 nm UV light was used as light source. In all cases of the experiments, the photodegradation of lindane in the sediment samples were fitted for pseudo-first-order kinetics.     

Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation

This work aimed to investigate the effectiveness of ultraviolet (UV) radiation on the degradation of the antimicrobial triclocarban (TCC). We investigated the effects of several operational parameters, including solution pH, initial TCC concentration, photocatalyst TiO₂ loading, presence of natural organic matter, and most common anions in surface waters (e.g., bicarbonate, nitrate, and sulfate). The results showed that UV radiation was very effective for TCC photodegradation and that the photolysis followed pseudo-first-order kinetics. The TCC photolysis rate was pH dependent and favored at high pH. A higher TCC photolysis rate was observed by direct photolysis than TiO₂ photocatalysis. The presence of the inorganic ions bicarbonate, nitrate, and sulfate hindered TCC photolysis. Negative effects on TCC photolysis were also observed by the addition of humic acid due to competitive UV absorbance. The main degradation products of TCC were tentatively identified by gas chromatograph with mass spectrometer, and a possible degradation pathway of TCC was also proposed.